Carbamaldoximes

ABSTRACT

Novel carbamaldoximes of the formula   WHEREIN Y is selected from the group consisting of hydrogen, chlorine and bromine and X is selected from the group consisting of phenyl optionally substituted with at least one member of the group consisting of halogen, cyano, -NO2, alkyl of 1 to 6 carbon atoms and alkoxy of 1 to 6 carbon atoms and nitrofuryl having fungicidal activity.

United States Patent Perronnet et al.

CARBAMALDOXIMES Inventors: Jacques Perronnet; Pierre Girault,

both of Paris, France Assignee: Roussel Uclaf, Paris, France Filed: Apr.26, 1974 Appl. No.: 464,473

Related U.S. Application Data Division of Ser. No. 408,744, Oct. 23,1973, Pat. No. 3,836,582.

Foreign Application Priority Data Nov. 6, 1972 France 72.39141 U.S. Cl260/347.7; 424/285 Int. Cl C07d 5/30 Field of Search 26O/347.7, 79, 566AC References Cited UNITED STATES PATENTS 12/1965 Heiss et al. 260/347]51 July 15,1975

Primary Examiner-Harry I. Moatz Attorney, Agent, or FirmHammond &Littell I 5 7 ABSTRACT Novel carbamaldoximes of the formula 2 Claims, N0Drawings CARBAMALDOXIMES PRIOR APPLICATION This application is adivision of U5. patent application Ser. No. 408,744 filed Oct. 23, 1973,now US. Pat. No. 3,836,582.

STATE OF THE ART US. Pat. No. 3,742,036 describes aldoximes of theformula Cl R wherein R and R, are lower alkyl and R is hydrogen or loweralkyl having biocidal, fungicidal or bactericidal properties but theseare chemically distinct from the compounds of formula I.

OBJECTS OF THE INVENTION It is an object of the invention to provide thenovel carbamaldoximes of formula I and a process for their preparation.

It is another object of the invention to provide novel fungicidalcompositions and to providea novel method of cornbatting fungi.

These and other objects and advantages of the invention will becomeobvious from the following detailed description.

THE INVENTION The novel carbamaldoximes of the invention have theformula wherein X and Y have the above definition. The reaction ispreferably effected in the presence of an organic solvent such astoluene or tetrahydrofuran and a tertiary base such as triethylamine orpyridine.

The aldoximes of formula II can be prepared by known methods such ascondensing hydroxylamine with the appropriate aldehyde.

The novel fungicidal compositions of the invention are comprised of aneffective amount of at least one compound of formula I and a carrier.The compositions can also optionally contain one or more otherpesticides or other products influencing the growth of plants.

The compositions may be in the form of powders, granules, suspensions,emulsions or solutions, containing besides the active ingredients,cationic, non-ionic or anionic surface active agents; inert powders suchas talc, clays, silicates, Kieselguhr, etc.; or a vehicle such as water.alcohol, hydrocarbons or other organic solvents, mineral, vegetable oranimal oils, etc.

The fungicidal powders used for foliar spraying preferably contain 25 to95% by weight of the compounds of formula I and the fungicidalcompositions used as foliar powders preferably contain 2.5 to 99% bywieght of the compounds of formula I.

An example of a composition for a foliar spray comprises 25% by weightof O-[ N- trichlorovinylcarbamoyl]-a,p-dichlorobenzaldoxime, 15% byweight of Ekapersol S (condensation product of sodium naphthalenesulfonate), 0.5% by weight of Brecolane NVA (sodium alkyl naphthalenesulfonate), 34.5% by weight of Zeosil 39 (precipitated synthetichydrated silica) and 25% by weight of Vercoryl S (colloidal Kaolin).

For the protection of paints against fungi, the active compound offormula I may be incorporated during grinding of the pigments. Theconcentration of the products of formula I is preferably 0.05 to 5% byweight of the paint. For example, 1% by weight of O-[N-trichlorovinylcarbamoyl]-a,pdichlorobenzaldoxime is added to thepigments during grinding to obtain a paint protected against fungi.

The novel method of the invention for killing fungi comprises contactingfungi with a fungicidal amount of at least one compound of formula I.The method is useful in agricultrue and in protecting paints.

In the following examples there are described several preferredembodiments to illustrate the invention. However, it should beunderstood that the invention is not intended to be limited to thespecific embodiments.

EXAMPLE 1 O-[N-trichlorovinylcarbamoyl] a,pdichlorobenzaldoxime 19 g ofa,p-dichlorobenzaldoxime [Farley, Proc. N. Dakota Acad. Sci., Vol. 13(1959), p. 61] and 20 g of trichlorovinyl isocyanate (US. Pat. No.3,468,923) were added to ml of toluene and the mixture was stirred for30 minutes at C. The toluene was removed by distillation under reducedpressure and the residue was added to petroleum ether (boiling point-6575C) containing 10% isopropyl ether. The crystals formed wererecovered by vacuum filtration and dried to obtain 27.2 g of O-[N-trichlorovinylcarbamoyl]-a,p-dichlorobenzaldoxime melting at 92C.

Analysis: C H Cl N O Calculated: %C 33.14 %H 1.39 %CI 48.92 %N 7.73

Found: 33.3 1.8 48.5 7.5

EXAMPLE I! O-[ N-trichlorovinylcarbamoyl1-5-nitro-furfuraldoximeAnalysis: C H Cl N O Calculated: %C 29.25 %H 1.22 %N 12.79 %C] 32.38Found: 29.3 1.1 12.5 32.3

EXAMPLE III The protective activity ofO-[N-trichlorovinylcarbamoyl1a,p-dichlorobenzaldoxime for paints againstfungi comprised incorporating ml of an acetone solution of the testcompound into 100 g of paint (oil or water base paint) to obtain aconcentration of 2,1,0.5 or 0.25% by weight of the active compound.Layers of paint were prepared by spreading the paint thus treated onpolyethylene sheets while the con- STACH YBOTR YS ATRA WATER BASE PAINTbefore washing trol layers were untreated. After drying at 24 to 48hours, the paint layers were removed from the polyethylene and were cutinto 5 X 2 cm pieces. The said test pieces of paint were placed indishes containing a gelose nutritive medium free from assimilable carbonand comprised of 3 g of ammonium nitrate, 0.5 g of magnesium sulfate,0.25 g of potassium chloride, 1 g of monopotassium phosphate, 15 g ofagar-agar and 1000 g of demineralised water. Before addition ofagar-agar, the pH was adjusted to 6-7. Each dish contained 2 test piecesand 4 tests were run for each concentration.

The test pieces were contaminated by placing on each test piece drops ofa fungi spore suspension of Penicillium luteum, Myrothecium verrucaria,Cladosporium herbarum, Stachybotrys atra, Paecylomyces Varioti,Pullularia pullulans, Trichoderma Iignorum, Chaetomium globosum andAspergillus niger. The samples were stored in a tropical room at C andrelative humidity for three months. The attack before washing and afterwashing (developments above all samples, developments by placement ofdrops; stains at the placement of the drops, no attack) was noted. Thewashing was for the purpose of eliminating the stains caused bysuperficial development of mould, which do not correspond to aneffective attack of the paint. The results of the following Tables ShOWthat the test compound has a good activity for protecting paints againstthe various moulds tested.

OIL-BASE PAINT after washing before washing after washing ConcentrationsM A 2 l 0,5 0,25 2 1 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25

Developement over all the test piece Developement at the placement ofthe drops Stains at the placement of the drops TOTAL PROTECTIONPAECYLOMYCES VARIOTI WATER BASE PAINT OIL-BASE PAINT before paintingafter washing before washing after washing Concentrations M A 1 0,5 0,252 l 0,5 0,25 2 1 0,5 0,25 2 l 0,5 0,25

Developement over all the test piece Developement at the placement ofthe drops Stains at the placement of the drops TOTAL PROTECTIONPULLULARIA PULLULANS Concentrations M A 2 1 TRICHODERMA LIGNORIUM beforewashing WATER BASE PAINT before washing WATER BASE PAINT OIL-BASE PAINTafter washing before washing after washing 0,5 0,25 2 1 0,5 0,25 2 l 0,50,25

OIL-BASE PAINT after washing before washing after washing ConcentrationsM A 2 l 0,5 0,25 2 l 0,5 0,25 2 1 0,5 0,25 2 1 0 5 0 25 Developementover all the test piece Developement at the placement of the dropsStains at the placement of the drops TOTAL PROTECTION CHAETOMIUMGLOBOSUM WATER BASE PAINT OIL-BASE PAINT before washing after washingConcentrations M A 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0.25

Developement over all the test piece Developement at the placement ofthe drops Stains at the placement of the drops TOTAL PROTECTIONASPERGILLUS NIGER WATER BASE PAINT OIL-BASE PAINT before washing afterwashing before washing after washing Concentrations M A 2 l 0,5 0,25 2 I0,5 0,25 2 l 0,5 0,25 2 I 0,5 0,25 Developement over all the test pieceDevelopement at the placement of the drops Stains at the placement ofthe rops TOTAL PROTECTION PENICILLIUM LUTEUM WATER BASE PAINT OIL-BASEPAINT before washing after washing before washing after washingConcentrations M A 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25

Developement over all the test piece Developement at the placement ofthe drops Stains at the placement of the rops TOTAL PROTECTIONMYROTl-IECIUM VERRUCARIA WATER BASE PAINT OIL-BASE PAINT before washingafter washing before washing after washing Concentration M A 2 I 0,50,25 2 I 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25

Developement over all the test piece I Developement at file placement ofthe drops Stains at the placement of the drops TOTAL PROTECTIONCLADOSPORIUM HERBARUM WATER BASE PAINT OIL-BASE PAINT before washingafter washing before washing after washing Concentration M A 2 l 0,50,25 2 l 0,5 0,25 2 l 0,5 0,25 2 l 0,5 0,25

Developement over all the test piece Developement at the placement ofthe drops Stains at the placement of the dro TOTAL PROTECTION appendedclaims.

We claim:

1. A compound of the formula where Y is selected from the groupconsisting of hydrogen, chlorine and bromine and X is nitrofuryl.

2. A compound of claim 1 which is O-[N-trichlorovinylcarbarnoyl]5-nitrofurfuraldoxime.

1. A COMPOUND OF THE FORMULA
 2. A compound of claim 1 which is O-(N-trichlorovinylcarbamoyl)-5-nitrofurfuraldoxime.